Mixtures of water-insoluble disazo dyestuffs



United States Patent ABSTRACT OF THE DISCLOSURE Water-insoluble disazo dyestufi mixtures consisting of two symmetrical dyestuffs and one asymmetrical dyestufi prepared by coupling tetrazotized 4,4'-diamino-3,3'-dichlorodiphenyl with a mixture of l-acetoacetylamino-Z- methoxybenzene and 1-acetoacetylamino-2,4-dimethylbenzene or with a mixture of 1-acetoacetylamino-Z-rnethoxybenzene and l-acetoacetylamino-2,5-dimethoxy-4chlorobenzene.

The present invention provides new water-insoluble disazo dyestuffs and a process for preparing them; more particularly, it relates to dyestutf mixtures of each time two symmetrical and one asymmetrical dyestuff of the formula OCH3 C1 0 CCH I C 1 I I l and OCH3 Cl (JO-CH3 3,361,736 Patented Jan. 2, 1968 in the presence of an organic solvent such, for example, as pyridine, quinoline or dimethylformamide. To improve the physical properties of the pigments it may be of advantage to heat, for example to boil, the coupling mixture for some time, while simultaneously adding small amounts of an organic solvent, for example pyridine, chlorobenzene or a phthalic acid dialkyl ester or a resin soap.

The two coupling components may be admixed with one another in various ratios, depending on the desired properties regarding application of the pigment to be prepared. For example, the coupling components may be mixed with one another in the ratios of 1:1, 2:1, 3:1, 5:1 or 9:1. The disazo dyestufi mixtures obtained consist each time of one asymmetrical and two symmetrical disazo dyestuffs, whose quantity in the dyestufi mixture depends on the coupling conditions and on the ratio of mixture of the two coupling components.

The disazo dyestuffs obtained are water-insoluble pigments which are distinguished by good fastness to light and to solvents. They are suitable for the dyeing of plastic masses, synthetic and natural resins, lacquers and lakeformers, for the dyeing of spinning masses as well as for the dyeing and printing of paper and textiles according to the known pigment printing and dyeing processes.

Owing to their excellent properties with regard to application, the new dyestufls are especially suitable for the manufacture of printing inks.

OCH; 00-0113 1 R1 (JO-CH in which R and R represent methyl groups and R represents a hydrogen atom, or R and R represent methoxy groups and R represents a chlorine atom.

It has been known that by coupling 1 mol of tetrazotized 4,4'-diamino-3,3'-dichlorodiphenyl with 2 mols of l-acetoacetylamino-Z-methoxybenzene or with 2 mols of l-acetoacetylamino-2,4-dimethylbenzene water-insoluble yellow 5 disazo dyestutfs are obtained which may be used as pigment dyestuffs for the dyeing of rubber, polyvinyl compounds, polystyrene and for the preparation of printing inks (of. Colour Index, second edition 1956, volume 2 and volume 3, and Supplement 1963, Permanentgelb GG=C.I. Pigment Yellow l7=C.I. 21,105, and Permanentgelb GR=C.I. Pigment Yellow l3=C.I. 21,100).

Now, it has been found that by coupling 1 mol of tetrazotized 4,4'-diamino-3,3-dichlorodiphenyl with 2 mols of a mixture of l-acetoa-cetylamino-2-methoxybenzene and l-acetoacetylamino-2,4-dimethylbenzene or with 2 mols of a mixture of 1-acetoacetylamino-Z-methoxybenzene and 1-acetoacetylamino-2,5-dimethoxy-4-chlorobenzene valuable yellow disazo dyestuffs are obtained the dyeing properties of which are superior to those of the known dyestuffs.

The new dyestufis are prepared according to known methods by coupling the tetrazotized diamine with a mixture of both coupling components, for example, in an aqueous medium, suitably in the presence of a nonionic, anion-active or cation-active dispersing agent or The following examples illustrate the invention bu 45 they are not intended to limit it thereto:

Example 1 21.8 parts by weight of l-acetoacetylamino-2,4-din1ethylbenzene and 21.6 parts by weight of l-acetoacetylamino- 0 Z-methoxybenzene were dissolved at room temperature, While stirring, in a mixture of 500 parts by volume of Water and 46 parts by volume of S N-sodium hydroxide solution. An aqueous solution of 2 parts by weight of the reaction product of about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol was added to the solution. The coupling components were then precipitated by the addition of 15 parts by volume of glacial acetic acid. The fine suspension thus obtained was combined with an aqueous solution of 55 parts by weight of crystallized sodium acetate. Coupling was effected at about 20 C., by adding to the suspension of the coupling components, While stirring, during about 1-l /2 hours, a solution of tetrazotized 4,4'-diamino-3,3'-dichlorodiphenyl (prepared by dissolution of 25.3 parts by weight of 4,4-dia'mino- 3,3'-dichlorodiphenyl in the form of the hydrochloride gel).

When coupling was completed, the mixture was stirred for one hour and combined with an aqueous solution of 7 parts by weight of calcium chloride; the coupling mixture was then heated to 95 C. and kept at this temperature for 20 minutes. The dyestuff that has formed was separated by filtration with suction, washed and dried.

A printing ink for graphical purposes prepared with the yellow pigment dyestufi thus obtained gave prints with a very high tinctorial strength. With regard to shade, these prints corresponded to the prints obtained with the dyestuff Permanentgelb GG (=C.I. 21,105), but their tinctorial strength was by about 30% higher than that of the latter dyestufl. Compared with the prints obtained with Permanentgelb GR (=C.I. 21,100), the prints produced with the dyestulf of the present Example 1 were more greenish and exhibited a higher transparency.

Example 2 The process was carried out as described in Example 1 and after completion of coupling, the reaction mixture was stirred for one hour. An aqueous solution of 7 parts by weight of calcium chloride and an aqueous solution of 11 parts by weight of resin soap were added to the coupling mixture; the coupling mixture was heated to 95 C. and kept at this temperature for 20 minutes. The dyestufi was then separated by filtration with suction, washed and dried. A yellow pigment dyestuif was obtained. A printing ink for graphical purposes prepared with this dyestuif gave prints of high tinctorial strength and greater transparency than prints made with the dyestuif of Example 1.

' Example 3 The process was carried out as described in Example 1, but using as the dispersing agent instead of the reaction product of about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol, the same quantity by weight of a dibutylnaphthalene-sulfonic acid. A yellow pigment dyestufi" was obtained which, incorporated into a printing ink for graphical purposes, gave prints of high tinctorial strength and of a transparency which was superior to that of prints made with the dyestufi of Example 1.

Example 4 327 parts by weight of 1-acetoacetylamino-2,4-dimethylbenzene and 10.8 parts by weight of l-acetoa-cetylamino- Z-methoxybenzene were dissolved at room temperature, while stirring, in a mixture of 500 parts by volume of water and 46 parts by volume of a 5 N-sodium hydroxide solution. An aqueous solution of 2 parts by weight of a reaction product of about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol was added to the solution. The coupling components were then precipitated by the addition of parts by volume of glacial acetic acid. The fine suspension thus obtained was then coupled in the course of ll /2 hours, at about C., with a solution of tetrazotized 4,4-diamino-3,3-dichlorodiphenyl prepared as described in Example 1, while keeping the coupling mixture weakly acid by the simultaneous addition of an aqueuos solution of sodium acetate. When coupling was completed, the mixture was stirred for 1 hour, then heated to 95 C. and kept for 20 minutes at this temperature; the dyestufi that had formed was separated by filtration with suction, washed and dried.

A yellow pigment dyestufi was obtained. A printing ink for graphical purposes prepared with this dyestufi gave prints of high tinctorial strength, whose shade was more reddish and whose tinctorial strength was higher than that of prints prepared with the dyestuff of Example 1.

Example 5 The process was carried out as described in Example 1, but using a mixture of 27.3 parts by weight of 1- 'acetoacetylamino-2,4-dimethylbenzene and 16.2 parts by into a printing ink. The prints prepared with this ink showed a higher tinctorial strength than the prints prepared with the dyestuft of Example 1.

Example 6 The process was carried out as described in Example 1, but using a mixture of 19.8 parts by weight of 1-acetoacetylamino-2,4-dimethylbenzene and 23.8 parts by weight of l-acetoacetylamino-2-methoxybenzene.

A yellow pigment dyestufi was obtained which exhibited very good properties with regard to application upon incorporation into a printing ink. The prints prepared with this ink were more greenish than the prints made with the dyestufi of Example 1.

Example 7 The process was carried out as described in Example 1, but using a mixture of 2.2 parts by weight of l-acetoacetylamino-2,4-dimethylbenzene and 41.3 parts by weight of 1-acetoacetylamino-2-methoxybenzene.

A yellow pigment dyestulf was obtained which, incorporated into a printing ink, gave greenish yellow prints and which had very good properties regarding application.

Example 8 39 parts by weight of l-acetoacetylamino-Z-methoxybenzene and 6 parts by weight of 1-acetoacetylamino-2,5- dirnethoxy-4-chlorobenzene were dissolved, at room temperature, in a mixture of 320 parts by volume of Water and 50 parts by volume of 5 N-sodium hydroxide solution. The solution was clarified by means of silica gel, and the filtrate was introduced at 0 C., in the course of about 30 minutes, into a mixture of 340 parts by volume of water, 18 parts by weight of glacial acetic acid and an aqueous solution of 1.5 parts by weight of the reaction product of about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol. The fine suspension obtained was then added, at 20 C., in the course of about 1 hour, a solution of tetrazotized 4,4'-diamino-3,3-dichlorodiphenyl (prepared by dissolution of 25.3 parts by weight of 4,4-diamino-3,3-dichlorodiphenyl in water with addi-' tion of 100 parts by volume of 5 N-hydrochloric acid, tetrazotization by means of 40 parts by volume of 5 N- sodium nitrite solution and clarification of the tetrazo solution by means of silica gel).

When coupling was complete, the mixture was stirred for 1 hour, an aqueous solution of 7 parts by weight of calcium chloride was added, the coupling mixture was heated to C. and kept for 20 minutes at this temperature. The dyestuflf that had formed was separated by filtration with suction, washed and dried.

A printing ink for graphical purposes prepared with the yellow pigment dyestutt thus obtained gave prints that had a high tinctorial strength. The shade of these prints corresponded to that of prints obtained with the dyestufi Permanentgelb GG (=C.I. 21,105), but the tinctorial strength of these prints was by about 30% higher than that of the latter prints.

Example 9 The process was carried out as described in Example 8 and when coupling was completed, the reaction mixture was stirred for one hour. An aqueous solution of 7 parts by weight of calcium chloride and an aqueous solution of 11 parts by weight of resin soap were added to the coupling mixture, the mixture was heated to C. and

kept for 20 minutes at this temperature. The dyestutf was then separated by filtration with suction, washed and dried. A yellow pigment dyestufi was obtained. A printing ink for graphical purposes prepared with this dyestufl gave prints of high tinctorial strength and of a transparency which was better than that of the prints prepared with the dyestufi of Example 8.

5 5 Example 10 in which R represents a member selected from the group The process was carried out as described in Example consisting of methyl and methoxy, R represents a mem- 8, but using a mixture of 21.6 parts by weight of l-acetober selected from the group consisting of methyl and acetylamino-2-methoxybenzene and 30 parts by weight chlorine and R represents a member selected from the of l-acetoacetylamino-Z,5-dimethoxy-4-chlorobenzene. A 5 group consisting of hydrogen and methoxy, with the yellow pigment dyestufi was obtained which exhibited very proviso that R and R represent methyl when R; stands good properties with regard to application on incorporafor hydrogen and that R and R stand for methoxy, tion into a printing ink. The prints prepared therewith when R stands for chlorine. were considerably more reddish than the prints prepared 2. A mixture of water-insoluble disazo dyestuffs conwith the dyestuff of Example 8. 10 sisting of dyestuffs of the formulae 0 0H; 01 01 v 0 OH;

I 0-011: (JO-CH3 I @NH-C OCH-N=N N=NCHC O-NH-Q CH; 01 01 OH; (I: O-GHa I I JO-3H3 I GIL-@NH-Q O-CH-N=N--N=NCHC ONH-CH3 and 0 CH; c1 01 CH3 3 0-011; I I 0-0113 NH-O ocHN=N-N=N0Ho O-NH- CH;

What is claimed is: 3. A mixture of water-insoluble disazo dyestuffs con- 1. Mixtures of water-insoluble disazo dyestufis consisting of dyestuffs of the formulae 0 CH3 C1 C1 0 CH3 I (I) O C Ha I I (JO-C Ha Q-NH-C O-CHN=N-N=NCHCH-NH 0 CH3 or 01 0 OH: I c 0-0113 I I o 0-011: (El-@NH-C O-CHN=N--N=NCHC O-NH- 01 (I) OH; OI CH3 and 0 CH: 01 c1 0 OH;

I (I)HOH3 I 00H= I Q-NH-O O-CH--N=N N=N-oH-o O-NH-Q-Ol sisting of two symmetrical dyestuffs and one asymmetrical 45 dyestufi of the formulae 0 CH; 01 01 0 CH3 o O-GH; I I 0 -03, I @NH-C OCHN=N-N=NOHG O-NHQ R1 c1 01 R, I (JO-CH3 I O-GHH I R =N--N=N ro ONHR2 R; 1 12 and 0 CH; 01 c1 1 (I) OCH3 I 0-0113 I @NH-C OCHN=N N=NCHC O-NH-Q-R:

References Cited UNITED STATES PATENTS 2,361,566 10/ 1944 Reynolds 260-176 2,657,204 10/ 1953 DeLucia et a1 260-176 2,739,146 3/ 1956 Weigele et a1. 260-17 6 2,984,660 5/ 1961 Ribka 260-176 3,030,354 4/ 1962 Ribk-a 260-176 3,218,311 11/1965 Forter et a1 260-161 FLOYD D. HIGEL, Primary Examiner. 

